Gear lubricant



Patented May 12, 1953 UNITED"STATES PATENT OFFICE GEAR LUBRICANT Ferdinand P. Otto and Leo W. Manley, Woodbury, and Ralph V. White, Pitman, N. J assignors to Snoopy-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application February 8, 1950, Serial No. 143,156

, comprised only of a petroleum fraction, is incapable of withstanding the enormous pressures encountered between engaged surfaces in various types of modern machinery, such as the hypoid gears used in motor vehicles. This fact has led to the development of so called extreme pressure lubricants. Such lubricants are composed of a lubricating oil base having incorporated therein a small amount of a chemical ingredient which will form, or which is capable of reaction under extreme pressure conditions to form, a lubricant film capable of withstanding these abnormally high pressures. The added ingredients are known to the art as E. P. (extreme pressure) additives, or E. P. bases. Among the substances which have been used for this purpose are sulfur, both free and chemically combined. Various chlorine and phosphorus compounds have also been used, principally chlorinated hydrocarbons and esters of various phosphorus acids. ingredients have also been employed. None of the E. P. base formulations proposed up to the present time, however, have proved satisfactory over the range of service conditions encountered in automotive hypoid gears. Thus, whereas one E. P. lubricant will provide satisfactory lubrication under conditions of high speed shook loading and another under conditions of low speed, high torque operation, no one lubricant has been found to give adequate lubrication protection under both of these types of service conditions.

It is the object of this invention to provide an E. P. lubricant which is capable of maintaining a lubricant film, and thus providing highly efiicient lubrication, under the extreme pressure conditions of both high speed and heavy load service. Other objects will appear from thefollowing detailed description of the invention.

The invention resides in our discovery of a unique combination of three base ingredients, which combination provides outstanding effectiveness as an E. P. additive for hypoid gear lubricants. These three ingredients are the following:

1. A chlorinated aliphatic material in which the more reactive part of the chlorine has been replaced with a thiocarbonate group.

2. An ester obtained by reacting two moles of comercial hydroabietyl alcohol with one mole of malic acid.

Combinations of these types of chemical 20 Claims. (Cl. 252--46.7)

3. A phosphorus acid ester obtained by reacting three moles of an alkyl-substituted phenol with approximately one mole of phosphorus pentoxide.

In order that our invention may be readily and fully understood, the several components which make up our novel extreme pressure lubricant will now be described in detail, including examples of procedures which may be followed in preparing these materials and test results demonstrating the outstanding effectiveness of the contemplated lubricant compositions.

LUBRICANT OIL BASE The oil which forms the major proportion, from about 85 to about 99 per cent, by weight, of the gear lubricant composition herein contemplated may be any suitable lubricating oil, such as an oil derived from the refinement of a petroleum crude oil. The viscosity of the oil may vary, depending upon the intended application of the finished lubricant, from about 1 to about 10,000 centistokes at 100 F. Particularly preferred for use in this invention, i. e. in the hypoid gears of automotive vehicles, are lubricating oils having viscosities from about 10 to about 1500 centistokes at 100 F. The oil should, of course, also be selected. on the basis of suitable pour point and viscosity index characteristics for the specific purpose intended, it being understood that the desired characteristics of the finished lubricant may be obtained by theaddition of lubricating oil additives known to provide the desired effects on these properties in the oil.

CHLORINATED ALIPHATIC COMPOUND- THIOCARBONATE REACTION PRODUCT As indicated hereinabove, this component of our composite additive is a polychlorinated aliphatic material, or a polychlorinated material predominantly aliphatic in nature, in which part of the chlorine is replaced by a thiocarbonate group.

The preferred procedure which may be followed in synthesizing this material involves substantial chlorination of an aliphatic compound or a predominantly aliphatic material, such as a petroleum naphtha, followed by reaction of the chlorinated material with an alkali or an alkaline earth metal salt of an alkyl thiooarbonic acid in such proportions and under such conditions that only part, preferably about one-third, of the chlorine (that is, the more reactive chlorine) is replaced by the alkyl thiocarbonate group.

In the chlorination step, the aliphatic material is chlorinated to such an extent that the final chlorinated product corresponds to a po1ychlor compound, and in the case of petroleum naphtha the chlorination is preferably carried to a point at which the product has an average composition corresponding to a tetra-chlornaphthe. In general, it may be said that chlorination should be carried to the point at which the chlorine content is from about forty per cent to about sixty per cent, although materials of lower and higher chlorine content may be used, depending upon the aliphatic constituent.

The range of aliphatic materials which may be chlorinated. as the starting material extends from ethane to petroleum wax, the former being a compound containing two carbon atoms and the latter being a predominantly aliphatic ma" terial corresponding to a compound having about twenty-four carbon atoms. We have found, however, that the extremely short-chain compounds, represented by the ethane, and the extremely long-chain compounds, represented by petroleum wax, are somewhat more dificult to react 'and'are somewhat less efficient in their effect in the final formulation than hydrocarbons of an intermediate range, and for this reason preference is given to aliphatic materials within the range of from about 5 to-about 15 carbon atoms, particular preference being given to petroleum naphtha. (or kerosene), a hydrocarbon material predominantly aliphatic in nature corresponding to a compound having about 10 carbon atoms and having a boiling range of from about 150 C. to about 275 C.

The thiocarbonate group which is used to replace a part of the chlorine is, as has been indicated above, derived from an alkali or alkaline earth metal salt of a thiocarbonic acid, preferably an alkyl thioca-rbonic acid. The thiocarbonate radical may be a mono-, dior trithiocarbonate, but in general preference is given to the dithiocarbonate (xanthate) compounds, characterized by the divalent group (OCSe). The tri-- thiocarbonate typ of compounds, characterized by the divalent group (CS3) have also been prepared and have been found to form effective e2:- treme pressure agents in combination with the chlorinated aliphatic material, but from the standpoint of odor and cost, preference is to products in which the thiocarbonate constituent is a xanthate (divalent OCSz) group.

As to the allzyl substituents in the thiocarbonate or Xanthate groups, which are substituted in the chlorinated aliphatic material, it is preferable that such substituents be derived from aliphatic compounds of relatively low molecular weight. There is no particular advantage to be gained by having long-chain alkyl group in the xanthate or thiocarbonate substituent from the standpoint solubility, etc, and the lower molecular weight 211K371 groups give a finished product in which the content of chlorine and characterizing divalent thiocarbonate groups (@205, OCSz, or CS5) is somewhat more highly concentrated.

As examples of the thiocarbonate or xanthate materials which may be reacted withchlorinated aliphatic materials to provid extreme pressure agents of the type contemplated by this inven tion, we may use sodium or potassium methyl, ethyl, propyl, isopropyl, benzyl, butyl, or amyl xanthates'or the corresponding mono or trithi'ocarbonates.

It is highly important, as. stated above, that the proportions of reactants used and the conditions of reaction be controlled so that the final product contains both chlorine and. thiocarbonate characterizing groups in chemical combination with the aliphatic hydrocarbon material. The relative amounts of chlorine and sulphur, or, more specifically, of chlorine and thiscarbonate characterizing groups, in the finished product may be varied over a relatively wide range, but in general it may be said that the inished product should preferably be one which contains from about twenty-five to forty per cent chlorine and from about seven to fiiteen per cent sulphur. Expressing the sulphur content as the equivalent amount of characterizing thiocarbonate groups present in the product, such preferred products are more accurately identified containing from about ten per cent to about twenty-two per cent characterizing dithiocarbonate or Xanthate (divalent OCSz) groups or from about seven per cent to about seventeen per cent characterizing trithiocarbonate (divalent 033) groups. For general purposes it be said that the characterising-thiocarbonate-groupcontent is preferably from about seven per cent to about twenty-two cent.

The reaction betcan the chlorinated aliphatic material. and the thio'carbonatc is preierably carried out in the presence of a relatively low boiling point solvent. For convenience in reaction and purification, the solvent is preferably one in which the chlorinated aliphatic material and the reaction product are highly soluble but in which the alkali thiocarbonate and the a chloride are of low solubility. As an example of such a solvent we have found acetone to be highly satisfactory. although other solvents, such as methyl ethyl lzetone, may be used. Alcohols may also be used as solvents in this reaction. Solvents such as acetone-and methyl ethyl lretone are particularly desirable since they permit the reaction to proceed but tend to precipitate residual alkali thiocarbonate and chloride, thus permitting the process to be performed and the product substantially purified. all. in one step.

The. general preferred procedure followed in eileoting the replacement of the more highly roactive chlorine in chlorinated aliphatic mate rials with the thiocarbonate group is to dissolve the chlorinated aliphatic material in the solvent and add the alkali alkyl. thiocarbonate in an amount sufficient to give a product having the desired chlorine and. sulphur ratio. Under the conditions of reaction which we employ we have prepared materials using irom'about one-fourth to about twice as much alhali thiocarbonate (xanthate) as chlornaphtha. The preferred ratio, however, is to use a weighted amount of alkali thiocarbonate corresponding to from about forty per cent to about seventy per cent of the weight of the chlornaphtha used. It will be understood, of course, that these ratios vary with other chlorinated aliphatic materials, depending upon their hydrocarbon and chlorine content,

and should also take into consideration the aliryl substituent which attached to the characterizing thiocarbonate group.

.As aforesaid, the preferred products contemplated by this invention are those obtained by replacing a part of the chlorine in chlorinated petroleum naphtha with an alkyl Xanthate group. These materials are preferred to others in this general class of materials because of their case of synthesis, their cost, etc. An exemplary procedure for preparing such a product, which we may term chlornaphtha-xanthate reaction product or xantho-chlornaphtha is the following:

EXAMPLE I ChZomaptha-aranthate reaction product A chlorinated naphtha was first prepared by chlorinating petroleum naphtha (Stoddard solinseam? vent) until it contained about fifty-four per cent by weight of chlorine. 200 parts of the chlornaphtha were dissolved in about 500 parts of acetone and placed in a reaction vessel heated by a water jacket and equipped with stirrer and reflux condenser. To this solution 120 parts of potassium ethyl xanthate were addedand the mixture held at boiling temperature with stirring under reflux for "about two hours. The resulting mixture was cooled to room temperature,

Variation in xanthate and chlorine content of the reaction product can be obtained by varying the degree of chlorination of the naphtha; by varying the amount of alkali xanthate used; and by varying the hydrocarbon substituent in the alkali xanthate. varyingchlorine and xanthate content are readily possible. In general, as indicated above, we prefer a product containing from about tenlper cent to about twenty-two per cent of the characterizing xanthate group and from about twenty-five per cent to about forty per cent of chlorme.

' Dihydroabietyl malate This material is prepared by reacting 2 moles of hydroabietyl alcohol with 1 mole of malic acid. The hydroabietylalcohol reactant used is the commercial mixture marketed by the Hercules Powder Co. This mixture of alcohols is comprised of three alcohols having the following structures:

CH3 CHzOH CH: CHzOH q i C Ha CH:

C H: C H3 CH3 CH: Dehydroabietyl alcohol Dihydroabietyl alcohol C H; C H; O H

CH5 CH3 Tetrahydroabietyl alcohol The average proportions by weight of these alcohols in the commercial mixture are: per cent dehydroabietyl, per cent dihydroabietyl and per cent tetrahydrobietyl. The commercial product also contains an average of {about 15 per cent of non-alcoholic materials, which is considered as being comprised chiefly of methyl esters of hydrogenated rosin and hydrocarbon occurring in hydrogenated rosin.

Thus products of widely 6 -('Ionsidering the average molecular weight of the alcohol portion of the commercial product which represents 1 equivalent of hydroxyl group, to be approximately 290, it is seen that since the mixture contains 15 per cent of non-alcoholic materials, then 341 grams will be required to provide one equivalent weight of the hydroxyl group. Consequently, when preparing dihydroabietyl malate from 0.375 mole of malic acid which contains two carboxyl groups, 0.75 mole, i. e. 341x0.75=255.7 grams of the commercial material will be required.

The following example will serve to illustrate a preferred procedure for preparing the dihydroabietyl malate ester.

EXAMPLE II Preparation of dihydroabz'etyl malate denser device (reflux water take-off) for removing Water from the reaction as it evolved as an azeotrope of water and benzene. The mixture was heated to 130-135 C. and digested at this temperature for hour. The reflux water takeoff was filled with benzene and an amount of benzene was added to the reaction mixture such that the solvent refluxed while the flask contents were at l30-135 C. After 6 hours of refluxing, 11 ml. of water had been collected and the solvent was removed by gradually reducing the pressure in the system. The solvent-free product was warmed to 130 C. and suction filtered to remove an estimated 5 grams of residue.

The filtered product had a neutralization number of 13.3, indicative of a neutral ester content of 89 per cent.

. Alloy! phenol-P205 reaction product This product may be prepared by reacting P205 with an alkylated phenol. The preferred alkylated phenols are mono-tertiary octyl phe-' nol and (ii-tertiary amyl phenol, although other alkylated phenols, such as di-secondary amyl phenol, cetyl phenol, octadecyl phenol and wax phenols can also be used. The products obtained with the latter compounds are, however, somewhat less effective than those obtained with the preferred reactants.

The reaction is carried out by heating the alkylated phenol with P205 at temperatures of from about C. to about 125 C. for several hours, preferably from about 1 to 15 hours. The preferred products are obtained when three moles of the alkylated phenol are reacted with approximately one mole of P205.

The following examples will serve to illustrate convenient procedures'for the preparation of our preferred materials.

EXAMPLE III Di-tertiary amyl phenol-P205 reaction product Reaction mixture:

Ditert-amyl phenoL. 468 grams (2 moles) P205 94.5 grams /3 mole) The diamyl phenol was placed in a 1-liter, 4 necked, round bottom flask containing a reflux condenser, thermometer and mechanicallydriven stirrer. After heating to C., P205 was gradually added over a 3-hour period. Following this, the, temperature was maintained 9 car operating undervery high speed conditions. The procedures followed in these tests were as follows:

HIGH SPEED BUICK TEST A Buick passenger car (1948) is used for this test. This is essentially a test to determine the performance of the rear axle lubricant under high speed road condtions. The Pennsylvania turnpike between the Carlisle and Bedford toll gates serves as the test course. The round trip distance is 160 miles.

The course is traversed for-the most part at a speed of 90-92 miles per hour, with occasional bursts of speed to 100-105 M. P. H. Rapiddeceleration and acceleration are practiced when entering and leavingthe 35 M. P. H. speed zones at the five tunnels and two toll houses. The average running speed for the course is 7'7 M. P. H.

The turnpike run of 5,000 miles under the above conditions constitutes the test on a new 20 must perform satisfactorily under these diverse conditions. During the mountain test the tooth loading reaches 10,000 inch pounds during ascent of the mountain, while in excess of 40,000 inch pounds is absorbed during descent in low gear. In the case of the CRC L--545 Test, 32,311 inch pounds of torque constitutes the load conditions of the gears.

Summarized in the accompanying table are the results obtained using the above-described tests on oil blends of the three component additives of the invention, as compared to blends of only one or two of the component additives in the oil. It will be noted that only the three component additive blends satisfactorily pass all tests.

The base oil used in the tests was a Mid-Continent SAE 90 grade oil. The additive concentrations are expressed in weight percentages based on the oil-free product. RX in the table signifies reaction product.

High Speed High Torque Buick High Addltlve Ori al on Plus Additive Test CRC' Low Speed Test s eed Road f Truck gm 14-19-646 ORG-L-ZO-545 p Test Axle Test (A) 5% RX Chlorinated Kerosene Plus K-Ethyl Xanthate. I (B) 1% Dihydroabietyl Malate Pass.... Pass Pass Good (Slight Surface (0) Ditertiaryamyl Phenol Distress Gears).

us 2 s. II 10% Chlorinated Kerosene Plus K-Ethyl do Fail (Surface Very Poor (Heavy Xanthate. Fatigue Rip- Wear and Surface ple and Ridge) Fatigue). (A) 5% RX Chlorinated Kerosene Plus K-Ethyl Xanthate. IIL (B) 1% DihydroabietylMal-ate. ..-.do Pass Excellentg (Negligible (C) 0.5% Monotertiaryoctyl Phenol Plus Surface Distress of (A) w X hl t a K Pl *ss a orma e erosene us 3. as W K-EthylXanthate. at L do F (A f (B) 0.5% Monotertiaryoctyl Phenol Plusfi Pprqma 1 2 5 X face Distress of (A) 5% RX Chlorinated Kerosene Plus Gears) V K-Ethyl Xanthate. do Good (B) 1%DihydroabietylMalate.

(C) 0.67% RX Wax Phenol Plus P2O5..-;. (A) 6% RX Chlorinated Kerosene Plus K-Ethyl Xanthate. VI (B) 1% DihydroabietylMalate..... do Do,

(0) 0.5% RX Di-Secondary Amyl Phenol DODGE TRUCK MOUNTAIN PROCEDURE A l -ton Dodge tractor-trailer unit, loaded" to 22,500 pounds gross vehicle weight, is used for this test. The vehicle operates over mountainous terrain on a prescribed test course between Hagerstown, Md. and Cumberland, Md. (Route U. S. 40). Much severe low speed, high torque service is imposed on both the coast side and drive side of the axle gear teeth throughout this test, mixed with some high speed, low torque running. A new differential assembly is installed in the truck for each run. A 3,000-mile test is suificient to reveal; the lubricating qualities of thegear oil, as de-; duced from gear tooth surface examination, conditionsof bearings and other parts and used oil analysis.

The mountain test is considerably more severe than the CRC L20545 High Torque Test not only with respect to higher tooth pressures under low speed conditions, but also because a considerable amount of the operation is under relatively high speed conditions andthelubricant;

"to about 14.5 per cent,

The component additives .of the invention may be blended in the lubricating oil either individually or they may be first mixed together to form the composite additive and then blended, as such, with the oil. We have found that the efiectiveranges of concentration (in weight per cent) for the individual additives are the following: (a) from about (1) per cent to about 10 per cent, preferably 5 per cent, of the chlorinated aliphatic compound-thiocarbonate products; (1)) from about 0.1 per cent to about 3 per cent of dihydroabietyl malate; and (c) from about. 0.1

per cent to about 1.5 per cent of the alkylated phenol-phosphorus pentoxide product. The total amount of additives within these ranges which we may use, therefore, is from about 1.2 per cent with the preferred amounts giving a total concentration of 6.5 per, cent. The composite mixture for addition to the oil in the latter concentration will, therefore, contain-the individual additive in the following proportions:

- Per cent (a) hlorinated aliphatic compound-thiocarbonate product 76.9 (b) 'Dihydroabietyl malate 15.4 (c) Alkylated phenol-P205 product 7.7

It is to be understood that the composite additive of this invention may also be added to the oil in concentrations greater than. the range the purpose of improving the character of the 7,

oil in respects other than its E. P. quality, such as resistance to corrosion, detergenoy, viscosity index, pour point, etc.

Having now fully described our invention, what we claim as new and patentable is:

1. An extreme pressure lubricating composition comprising a major proportion of a mineral lubrieating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically subg stituting a part only of -the chlorine in a chlorinated aliphatic hydrocarbon material having from 2 to about 24 carbon atoms with a thiccarbonate group, (b) from about .1% to about 3% of dihydroa-biety-l mala-te-and o) from about 0.1% to about 1.5% of the reaction product formed by reacting 3 moles of an alkylated phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 'C.

2. An extreme pressure lubricating composition comprising amajor proportion of a mineral lubricating oil and minor proportions or addition agents asfollows z (a) from about 1% to about 10% of a product obtained; by chemically substitutin'g a part only of the chlorine in a chlorinated aliphatic hydrocarbon material having from 2 to about 24 carbon atoms with a anthate group, (b) from about 0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product formed by reacting 3 moles of an alkylated phenol with about 1 mole of phosphorus mentoxide, at atemperature of from about 75 C. to about 125 C.

3. An extreme pressure lubricatingcomposition comprisinga major proportion ora mineral lubrieating oil and minor proportions addition agents as follows: (a) rrom about.1 to about 10% of a product obtained by chemically sube stituting -a part only of the chlorine in a f/17110! rinated aliphatic hydrocarbon having from about 5 to about 15 carbon atoms with a thi ocarbonat'e group, (b) from about-0.1% to about 3% *of die hydroabietyl *malate and. '(c) -r"rom about era, to about 1.51% of the reaction product formed by reacting 3 moles of an alkylated phenol with about 1 mole of phosphorus pentoxide, at a tern-v perature of from about 75 C. to about 125 C.

4. An extreme pressure lubricating composition comprising a major proportion of a mineral :l-ubrb cating oil and minor proportions of addition agents as follows: (a) from about 1% to about or a product obtained by chemically substituting a part only or the chlorine in a chlorinated aliphatic hydrocarbon having "ii-om about 5 to about carbon atoms with a xanthate group, (b) from about 0.1% to about 3% of dihydro abietyl-malate-and (c) iromabout 0.1% to about 15% of the reaction product formed reacting 3 moles of an alkylated phenol wi lhabout 1 mole of phosphorus pentox-ide, at a temperature oi from about 75 C. to about 125 C.

'5. An extreme pressure lubricating composition comprising a major proportion "of a mineral lubricating oil and minor proportions of "addition agents as follows: (a) from about 1% to about 10% 01 a product obtained by chemically substituting a part only or the chlorine in a chlorinated petroleum naphtha with a thiocarbonate group, such product having a chlorine content or from about to about and a characterizing thiocarbonate group content of from about *2 to about 22%, (b) from about 0.1% to about 3% of dihydroabietyl (c) from about 6.1% to about 1.5 of the reaction prod t formed by reacting 3 moles of an alkylated phenol with about 1 mole of phosphorus pentoxide, at a temperature oi from about C. to about C.

6. An extreme pressure lubricating composi- Y tion comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follow: (a) from about 1% to about 10% of a product obtained by chemically sub stituting a part only of the chlorine in a chlorinated petroleum naphtha with an alliyl Xanthate group, said product having a chlorine con tent of from about 25 to about 40% and a characterizing Xanthate group content or from about 10% to about 22%, (b) from about 0.1% to about 3% of 'dihydroa-bietyl malate and ('c) from about 0.1% to about 1.5% of the reaction product formed by reacting 3 moles of an alkylated phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

7. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) f-romabout 1% to about 10% of a product obtained chemically substituting a part only of the chlorine in a chlorinated aliphatic hydrocarbon material having from 2 to about 24 carbon atoms with a thiccarbonate group, (b) from about 0.1% to about 3% or dihydroabietylmalate and (c) from about 0.1% to about 1.5% or'the reaction product produced by reacting 3 moles or ditertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

8. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricatingoil andminor proportions of addition agents as follows: (a) from about 1% to. about 10% of a product, obtained by chemically substituting a part only or the chlorine in a chicrinated aliphatic hydrocarbon material having from 2 to about 24 carbon atoms with "a thiccarbonate group, (b) from about 0.1% to about 3% or 'dihydroabietyl'malate and '(c) from about 0.1% to about 1.5% or the reaction product produ'ced by reacting 3 moles of monotertiary octyl phenol with about 1 mole "of phosphorus pentoX-id'e, at a temperature of from about 75 C. to about 125 C.

9. An extreme pressure lubricating composition comprising-a major proportion of a mineral lubricating oil and minor proportions or addition agents as follows: (a) from about 1% to about 10% of a product obtained chemically substituting a partonly "or the chlorine in a chlorin'at'ed aliphatic hydrocarbon material having from 2 to about 24 carbon atoms with a thicca'rbona'te group, (b) froma bou't 0.1%-to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1. 5% df'the reaction prod-not pro duced by reacting 3 moles or wax phenol with about 1 mole of phosphorus pentox'ide, at a temperature of from about 75- C. to about 125 C.

10. extren'ie pressure lubricating composition'comprising a major proportion of a mineral 5513 lubricating .oil and .minor propb'rtionsbf addition agents .as. follows: (a): .from about v 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated aliphatic hydrocarbon having from about to about 15 carbon atoms with a thiocarbonate group, (b) from about 0.1% to about:.3%..of 1dihydroabietyl malate and-1c) ".fromiabout. 0.1% to about 1.5% of the reactionzproduet produced'by reacting 3.moles of ditertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about'75 C. to about 125 C.

11. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows-:- (a) from about 1% to about of a product obtained by chemically substituting a part onlyoi the chlorine in avchlorinated aliphatic hydrocarbon having from about 5 to about carbon atorns with athiocarbonate group, (b) from about 0.1% to about 3% of dihydroabietyl malate audio) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of mono-tertiary octyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

12. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated aliphatic hydrocarbon having from about 5 to about 15 carbon atoms with a xanthate group, (b) from about 0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of ditertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

13. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated aliphatic hydrocarbon having from about 5 to about 15 carbon atoms with a xanthate group, (b) from about 0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of mono-tertiary octyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

14. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated petroleum naphtha with a thiocarbonate, said product having a chlorine content of from about 25% to about 40% and a characterizing thiocarbonate group content of from about 7% to about 22%, (b) from about 0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of ditertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

15, An extreme pressure lubricating compositionzcomprisinga major proportion of a mineral lubricating; oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated petroleum naphtha with a thiocarbonate, said product having a chlorine content of from about 25% to about and a characterizing thiocarbonate group content of from about 7% to about 22%, (b) fromabout.0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of mono-tertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

16. .An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of additionagents as follows: (a) from about 1% toabout 10% of a product obtained by chemicallyv substituting a part only of the chlorine in a chlorinated petroleum naphtha with an alkyl xanthate group, said product having a chlorine content of from about 25% to about 40% and a characterizing xanthate group content of from about 10% to about.22%, (b) from about 0.1%

to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of di-tertiary amyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about C.

17. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated petroleum naphtha with an alkyl xanthate group, said product having a chlorine content of from about 25% to about 40% and a characterizing xanthate group content of from about 10% to about 22%, (b) from about 0.1%

to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of monotertiary octyl phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

18. An extreme pressure lubricating composition comprising a major proportion of a mineral lubricating oil and minor proportions of addition agents as follows: (a) from about 1% to about 10% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated petroleum naphtha with an akyl xanthate group, said product having a chlorine content of from about 25% to about 40% and a characterizing xanthate group content of from about 10% to about 22%, (b) from about 0.1% to about 3% of dihydroabietyl malate and (c) from about 0.1% to about 1.5% of the reaction product produced by reacting 3 moles of wax phenol with about 1 mole of phosphorus pentoxide, at a temperature of from about 75 C. to about 125 C.

19. A mineral lubricating oil concentrate including a major proportion of a mineral lubrieating oil and a minor proportion, upwards of about 15% by weight, of a composite mixture of the following materials: (a) about 76.9% of a product obtained by chemically substituting a part only of the chlorine in a chlorinated aliphatic hydrocarbon material having from 2 to 15 about 24 carbon: atoms. with a thiooarbonate group, (b) about 154% of dihydroabietyl mailate and about 7.7% of the reaction product formed by reacting 3 moles of an alkylateup'henol with about 1 mole of phosphorus. pentox-tde, at a temperature of from about C; to about 125 C.; said minor proportion being of such magnitude that when saidconoentrate is-bilended with mineral lubricating oil, the resultingz'mim eral lubricating oil will cont-am between Y 1 1% and about 15% by weight of said composite mixture.

20. A mineral lubricating" oil concentrate including' a major proportion of aminemt lubrieating oil and a minor proportion, upwacds of about 15% by weight, of a composite-mixture of the following materials: (a) about f7,9 of a product obtained by :chemioaily substituting a part only of the chlorine in a chlorinated petroleum naphtha with an alkyl xamshate group; said. product having :a chlorine content of from about to about 40% and 'aohamoterizing xanthate group content of about 10% to ab'out 22.95;, i b) about line s oftlihydroabietyl malate and 0-) abput 7;!'l"% oi thereaction product produced by'raaofing'ii molessof mono-tertiary octyl phenol with about; L mole of phosphorus pentoxide, ate temperature ofxfrom about C. to about. 1%? C.; said minor proportion being of such magnitude that when said concentrate is blendect with mineral lubricating: oil, the resultmineral lubricating oil will contain between about 1*%. and about by weight of said composite mixture.

FERDINAND P. OTTO.

LEO MANLEY.

V. WHITE.

References? Cited in the file of this patent UNTIED STATES PATENTS Numbeit' Name Date '2', 1'33,'31.1 Shuman: Oct. 18, 1938 2153395 Berger Apr. 4, 1939 2,384,595, Blair, Jr Sept. 11, 1945 2343,5791 Fuller June 15, 1948 

1. AN EXTREME PRESSURE LUBRICATING COMPOSITION COMPRISING AN MAJOR PROPORTION OF A MINERAL LUBRICATING OIL AND MINOR PROPORTIONS OF ADDITION AGENTS AS FOLLOWS: (A) FROM ABOUT 1% TO ABOUT 10% OF A PRODUCT OBTAINED BY CHEMICALLY SUBSTITUTING A PART ONLY OF THE CHLORINE IN A CHLORINATED ALIPHATIC HYDROCARBON MATERIAL HAVING FROM 2 TO ABOUT 24 CARBON ATOMS WITH A THIOCARBONATE GROUP, (B) FROM ABOUT 0.1% TO ABOUT 3% OF DIHYDROABIETYL MELATE AND (C) FROM ABOUT 0.1% TO ABOUT 1.5% OF THE REACTION PRODUCT FORMED BY REACTING 3 MOLES OF AN ALKYLATED PHENOL WITH ABOUT 1 MOLE OF PHOSPHORUS PENTOXIDE, AT A TEMPERATURE OF FROM ABOUT 75* C. TO ABOUT 125* C. 